Sulphur dyestuffs



Patented Dec. 17,1946

UNITED STATES PATENT OFFICE 2,412,922 SULPHUR DYESTUFFS Norbert Steiger,Lock Haven, Pa., assignor to American Aniline Products, Inc., New York,N. Y., a corporation of New York No Drawing. Application February 8,1944,

Serial No. 521,571

NHe

The condensation is eiiected with chloranil in alcohol.

2 amino 3 mercapto diphenyl can be obtained by a caustic fusion of 2amino 4 phenyl benzothiazole which is prepared in good yield from 2amino diphenyl thio urea by treatment with halogens or acid halides inany one of the many ways given in the chemical literature for thepreparation of 2 amino aryl thiazoles. (See Organic Synthesis, vol,22,'p 16; Hunter, Journal Chemical Society, 1926, p, 1399; Friedlaender,

' Fortschritte der Teerfarben Fabrikat on, Berlin (Julius Springer1932), vol. 1'7, page 613D. R. P. 537,105; vol. 21, Berlin (1937), page227-D. R. P. 604,639.)

The invention will be more clearly understood by reference to thefollowing examples which are given merely as illustrations of the methodand not as limitations on the invention. The parts are by weight.

Example 1 36 parts Cellosolve (ethylene glycol monoethyl ether), 290parts water, parts sodium sulphide cone, 31 parts sulphur, are heated tosolution in a stainless steel kettle provided with an agitator andreflux condenser, thus producinga polysulphide of approximate formulaNazSae. Then are added at 60 degrees C. 20 parts 5 phenyl1.3.4.trichloro-phenthiazone. The temperature of the mass is increasedwithin four hours to the boil, then kept refluxing 36 to 48 hours. Themelt is then diluted with 2500 parts of water, 20 parts soda ash areadded and aerated at 50 to degrees C. The dyestufi is filtered, thefilter cake sludged with 1000 parts water acidified with hydrochloricacid, filtered and the cake washed acid-free with water and dried. Thedyestufl is, when ground, a brown powder which is easily so1-, uble indiluted sodium sulphide solution. From this solution cotton is dyed inbright, reddish brown shades of excellent fastness to washing, goodfastness to chlorine, and very good light iastness.

The Cellosolve can be replaced as well by glycerine, ethylene glycol,diethylene glycol, etc. The melt can also be carried out in water.alone, but in this case the melting time has to be extendedappropriately.

Example 2 A solution is. madenup of 48 parts sodium sulphide c0110., 3parts sulphur in parts water.

obtained dyestufi is readily soluble in diluted aqueous sodium sulphidesolution and dyes full brown shades on cotton, which are not quite asbright but are more yellowish than those dyeings obtained with thedyestuff from Example 1.

Example 3 A stainless steel kettle, equipped with agitator and refluxcondenser, is charged with 200 parts normal butanol, 96 parts sodiumsulphide, 66 parts sulphur and boiled for A to 1 hour. It is then cooleddown to 90 degrees and 50 parts phenyl 1.3.4.trichloro-phenthiazone areadded and refluxed for 36 hours. The butanol is steam distilled off, thedyestuff is salted out, filtered, and the filter cake washed with saltwater. The excess sulphur can be removed in the usual manner, e. g., byextraction with an aqueous solution of sodium sulphite. The ground, drydyestufi is a dark brown powder.

brown of excellent fastness, somewhat bluer in shade than the dyestufiof Example 1, Similar dyes are obtained by using higher polysulphides,e. g., NazSs or NazSr.

Example 4 20 parts sodium sulphide cryst., parts water, 25 parts sulphurand 10 parts 5 phenyl 1.3.4.trichloro-phenthiazone are intimately mixedand dried in vacuum. The mixture is then baked at 185 to 200 degrees C.,until the H2S evolution has ceased. The melt is pulverized and dissolvedby heating with a sodium sulphide solution. The dyestufi is thenisolated by aeration. It dyes cotton from the sodium sulphide bath infull brown shades of very good fastness.

Example 5 A stainless steel kettle is charged with 200 parts alcohol, 31parts sulphur, 21 parts sodium sulphide and refluxed 1 hour. Then areadded 18 parts 5 phenyl 1.2.4.trichloro-phenthiazone and the wholerefluxed for 60 to 72 hours. After this time, parts sodium sulphide, 300parts water, 1- part of Filter-Gel are added and the solution filteredat 80 degrees C. 10 parts soda ash are added to the filtrate andaerated. The dyestuif is then filtered and dried. It is, when ground, adark brown powder, easily soluble in sodium sulphide and dyes thevegetable fibers a bright reddish brown of excellent fastness.

Example 6 The thionating stainless steel vessel is charged with 30 partsCellosolve, 70 parts water, 46 parts sodium hydroxide, 92 parts sulphur,and heated under reflux to solution. Then are added parts 5 phenyl1.3.4.trichloro-phenthiazone and refiuxed 48 hours. The temperature ofthe melt is about 108 degrees C. The melt is diluted with a solution of20 parts sodium sulphide in 300 parts water, refluxed 1 hour andfiltered. The dyestufi is'is'olated by aeration of the filtrate. The dyeyields, when dyed from the sodium sulphide bath, a bright, reddish brownon cotton.

Having thus described my invention, what I claim is:

1. A sulphur dye resulting from the thionation It dyes the vegetablefibers from a sodium sulphide bath, a bright reddish or 5 phenyl1.3.4.trichlorophenthiazone 2 corresponding to the following formula:

by acting with an alkali metal polysulphide on said compound at theboil; said dye being a water insoluble thionated compound which issoluble in dilute aqueous sodium sulphide solution and which dyesvegetable fibers from an aqueous sodium sulphide solution in shadesthat'develop in air to a brown.

2. As a sulphur dye intermediate the 5 phenylol.3.4.trichlorophenthiazone 2 represented by the following formula:

3. The process which comprises thionating in a thionating medium acompound represented by the formula:

said thionating medium consisting of higher alcohols and a polysulphiderepresented by the formula NazSe, wherein an is at least 3; heating insaid medium until said compound is thionated and then distilling ofi thesolvent in vacuum,

steaming the residue and salting out the dye from the residue.

5. The process which comprises the thionation of a compound representedby the formula:

6 ing a solution of sodium sulphide, sulphur and water, and addingthereto alcohol and 5 phenyl 1.3.4.trichlorophenthiazone correspondingto the formula:

refluxing at the boil for from 36 to 48 hours, di-

luting the melt with water, arid isolating the dyestufi in the usualmanner.

NORBERT STEIGER.

